Precisely Tailoring the Architecture of Metal-Quinone Networks via a Template-Directed Coordination Assembly

Microarchitected materials with programmable topological configurations provide a versatile platform for enhancing functionalities and broadening applications in advanced materials science. Metal-quinone networks (MQNs) uniquely combine the inherent bioactivity of natural quinones with the structural tunability of framework-based materials, conferring integrated advantages, including high drug-loading capacity, bidirectional pH responsiveness, extensive adhesion capability, and ease of modification. However, the achievable dimensional range of MQNs through existing synthetic approaches remains limited, restricting precise control over their structural characteristics. Here, we present a strategy involving prepolymerization of natural quinones, followed by the construction of rodlike micelles and metal-coordination assembly, to achieve precise morphological control of MQNs. By systematically varying parameters including ligand-to-metal ratio, solvent types, surfactant types, and cross-linking agents, a series of MQN architectures such as book-, sheet-, thread-, spindle-, and rodlike structures were obtained. Moreover, the morphology progressively evolves from one-dimensional (1D) rod- and needle-like structures to three-dimensional (3D) rectangular blocklike forms. Notably, the rod-shaped MQNs exhibit tunable aspect ratios ranging from 3.0 to 80.0. Scanning electron microscopy (SEM) characterized solvent-induced facet-selective growth and stoichiometrically dependent anisotropic growth, thereby enabling predictable control over the geometrical shape. The findings of this work provide guiding insights into the rational construction of sophisticated structures of MQNs for potential applications.